Process for manufacturing nitko-



I Patented Aug. 15, 1933 PROCESS iron MANUFACTURING Nrrno- COMPOUNDS or James F. OBrien, Seattle, Wash.

" No Drawing.

Application December 'Serial No. 241,463

. 2 Claims. (01. 260 -142) f .This invention relates to a process formanufacturing Intro-compounds from coal tar oils and relates more particularly to a process for nitrating and refining the light oil obtained from 5 coal tar distillatiomat temperatures from 95 to 115 Centigrade, whereby such oil may be 7 utilized as a hydro-carbon for explosives employing oxidizing bases, such as salts of alkaline metals, ammonium, or the'like.

10 The primary "aima'nd fundamental object of the present invention is the provision of a low temperature nitration process for treating light oil of coal tar, whereby a greater yield of low 7 V freezing and water-proofing properties and quah l5 ities for the refined nitrated product is obtained.

' f'Ihe present process contemplates increasing the specific gravity of the light 'oil by the reflux distillation process; removing. the fatty matter contained therein nitrating the refined oil liquor at low temperatures combined with rapid increases of temperatures after nitration 3 and the retention of such increased temperatures for predetermined periods; neutralizing the nitratedoilpand finally washing the'same, all of which are important features and objects of the" invention and are to be correlated in the broad aim of enhancing the efficiency of the process for general use, and for producing a hydro-carbon for explosives which will remain" liquid at all ordinary temperatures. 7

The above, and additional features, purposes and advantages, which will hereinafter be more specifically treated, are attained in the manner. set forth in the following specification and then more clearly pointed out in the claims which are appended hereto and form part of this application. r

Before taking up the detailed description .of

the process and product evolved by the present invention,'a general exposition of the advantages and benefits to be derived therefromwill be undertaken. l V I 'Heretofore mononitrotoluol, dinitrotoluol and trinitrotoluolhave been generally employed as hydro-carbons for chloratedexplosives, and in their commercial :form ordinarily *contain certain" substances having no essential value, insofar as the 'efiiciency' ofthe explosives is concerned, and for this reason have, in some instances, been 'rially affect their water-proofing and low freez- :bodiment, the light oil distilled from co'al'tar at used to the extent of 90% filler. Further, the

ling properties and qualities. It is' therefore, a i

primary object of this invention; to provide a process fortreating'the light oil obtained from coal tar at temperatures between 95 to 115 Centigrade and having an average specific gravity of approximately .862, whereby a novel liquid hydro-carbon is produced, which is neither a mononitrotoluol, dinitrotoluol, or trinitrotoluol, but which possesses greater Waterproofing prop-o erties and the same non-freezing properties as dinitrotoluol, and which may be employed as an In carrying out the process in its preferred emtemperatures from 95 to 115 Centigrade and havingan average specific gravity of approximately '.862, is first treated by the reflux distillation process to raise its specific gravity to .904, and for this purpose a vacuum still having a reflux condenser, a steam coil and cooling coil is employed and charged with the light oil to be treated. A loss of approximately 20 of light oil volume occurs during distillation, so that a specific gravity of .904 is'obtained for the resultant oil liquor; which is then subjected to the-action of to 1% strong sulphuric acid solution to destroythe foreign fatty matter contained therein; then cooled off to approximately 20 Centigrade, then prenitrated with a solution of nitric acid, sulphuric acid and water in the following proportions H2SO4, 20% ENG: and 10% E20, the amount'employed being 5% by'volume of oil liquor. slowlyand the temperature of the oil liquor during this time must not exceed-20 Centigrade,

and when the desired amount of acid solution has been added, the temperature of the oil liquor and acid mixtureis increased to "10 Centigrade for one-half hour, following which it is decreased to 30 Centigrade, I

The oil liquor is then allowed to settle and the spent ac'id'is run off, then-the oil liquor is treated with a 2% solution of caustic soda,- then it is washed with water in the following proportions, 10 partsof Water to l part of'oil-liquor', following which-it is allowed to completely settlefor approximately'eight hours,. at which time prenitration of the same is completed. J I

The prenitrated oil liquor is next blown to a gravity feed tank above a'nitrating vessel, which latter is charged with an acid solution consisting of 60% H2504, 35% I-INO and 5% H2O. -.The prenitrated oil liquor is slowly added to the acid solution, in the proportion of A; oil liquor 16% 1 theI-INO: (1.44); employment 'ofrefiux'distillaacid solution; the temperature being maintained at 20 Centigrade and when all of the oil liquor has been added the temperature is increased by means of a steam coil in the nitrating vessel to Centigrade for approximately one-half hour, the intermixed charge being kept in motion during' this time, following which the same is cooled to 20", Centigrade, and is then allowed to settle for approximately four hours. The dinitrated oil liquor is then drawn 01f into a neutralizing tank and is washed with a 2% to 5% neutralizing solution, such as caustic soda, soda carbonate, or lime, until a neutral point is reachedfollowing which the neutralized-dinitrated oil liquor is washed with hot water at 65 Centigrade for approximately one-half hour, after which it is allowed to settle for approximately two hours,

this completes the nitration process. In this connection I desire to state, that the spent acids upon completion of the dinitrating of the oil liquor are vrun .ofi to-a rectifying tank and are used again for the prenitration of succeeding charges of oil liquor. 1 I

* vThe resultant dinitrated product, which I have elected to name Toluite is neithera-mono-n 1- The. ,Toluite of the invention contains all of the waterproofing and low freezing properties and qualities of ortho-nitrotoluol and para-nitrotoluoland at the same time the benzol and benzene elements are not in ratio to be harmful to the strength of the explosives with which the =-I.oluite is used, nor does actual experience show that the flame, of such explosives is increased.

The. essentials and. important features of the present process and product are the specific gravities of the light oil (.862) the H2SO4 (1.84) and tion,'and the employment of lower temperatures of nitration, as compared with'the distillation methods and higher temperatures, ofnitration heretofore employed in other nitration processes. Actual, experience has demonstrated that the lower the point of nitration the greater the yield of 'low freeZing and Water-proofing properties and qualities of the resultant product, and by rapidly increasing the temperatures and holding same for predetermined periods after nitration, in' accordance "with the time-temperature steps herein setforth, the larger final yield of refined di-nitrated oil liquor is obtained. The yield of refined diriitr'ated oil liquor to the raw oil should be substantially in the ratio, of one and one-half gallons of refined oil to one gallon'of raw or light oil, dueprimarily to'the absorption or the incorporation of. acids therewith while being treated.

' In the production or manufacture of explosivesthe novel dinitrated oil productor hydrocarbon Toluite functions as the sensitizing agent therefor, and for this purpose is intimately intermixed with oxidizing agents, such as chlorates or perchlorates of alkaline metals, or of ammonium, together with carbonaceous substances,

and jwith or without. nitrates of the alkaline metals, or of ammonium and with orwithout're strainers, such as silico-aluminous substances and carbonates of the alkalineearths, and with or without further water-proofing agents, such as collodion or collodion cotton, and with or without agents, such as dehydrated sodium carbonate in powdered form, whereby the deliquescent salts, occurring as impurities in the said chlorates and perchlorates, are converted into non-deliquescent saltswhich will not subsequently absorb water and thereby materially affect or injure the quality of the explosives. While the primary function of the Toluite in the explosives is to sensitize the oxidizing agents or substances in their general explosive reaction, as above described, it also serves due to-its oily nature to desensitize said agents against mechanical friction during processing of the explosive by coating or insulating the crystals of the same, whereby the resultant explosive compounds possess the following inherent quaiities and attributes: they cannot cury caps of high power, as for example 6 x oaps,3 *for detonation either confined or unconfined; are

substantially smokeless, except for minimum amounts of non-injurious fumes; are easily, safely and economically manufactured andprepared for commercial use in the form of plastic car- If 'tri'dges or sticks of suitable consistency in various degrees of strength and speed of detonation from the range of black powder to that of high explosives, and are adaptable for hard rock mining, stump blasting, road work, quarrying, tree planting, ditching, breaking up hard-pan, bullas a low frame powder for coal-mining, and beingsubstantially free from noxious gases or fumes, as above mentioned, are especially adaptable and desirable for use and employment in constricted and confined spaces.

To further increase the speed of detonation of the explosives herein described I may elect to combine therewith an additional hydro-carbon or nitro-compound, such as trinitrotoluene, nitroglycerine or the like, which compounds are intimately intermixed with the ToluiteVprior to its incorporation with the correlated oxidizingagent thereof.

Sawdust '7 Wherefore, it will be manifest and apparentto' those skilled in the art upon an understanding of the foregoing, that the'present application is predicated upon the disclosure of a process for.

manufacturing nitro-compounds from light oils distilled from coal tar at temperatures ranging between 95 to 115 Centigrade and having an average specific gravity of approximately .862: which contemplates employing reflux distillation of such oils; nitration of the same at low temperatures combined with rapid increases of temperatures after nitration and the retention of such increased temperatures for predeterminedperiods, thus evolving a novel time-temperature nitration method for the production of a novel nitro-compound therefrom having agreater percentage of Waterproofing and non-freezing properties and qualities than heretofore obtained, and which will remain liquid at all ordinary temperatures. The invention further contemplates, the disclosure of explosive compounds embodying the novel nitrocompound hereinbefore described, which latter,

due to its specific characteristics, interacts when combined or intimately admixed with certain-spe- V cific oxidizing salts and other suitable ingredients to produce essentially new explosive compounds possessing certain novel characteristics in both their static form and their explosion.- However, it is to be understood that the invention resides in the novel compositions of matter having these distinctive attributes, and that they therefore-are not limited to the particular ingredients herein mentioned, or their specific proportions, as I am aware that substitutions may be made in the con-,

stituent ingredients, and variations in their proportions without, essential modification of the resulting compositions. The relative proportions of the several ingredients may be varied within reasonable limits according to the special application f-or which the explosive is desired, as in some instances a high explosive is necessary, while,

centigrade to produce a lightoil therefrom hay ing an average specific gravity of approximately proximately two' hours.

oil by reflux distillation to approximately .904,

successively nitrating said light oil at a temperature not exceeding 20 Centigrade with acid solutionsconsisting of nitric acid, sulphuric acid and water, rapidly increasing the temperature of the oil to approximately centigrade after each nitration step and maintaining such temperature in each instance for approximately one-half hour, coolingthe treated oil following each nitration step to a temperature not exceeding 30 Centigrade, separating the treated oil from the spent acids after each nitration, treating the nitrated oil after each nitration step with neutralizing caustic soda solutions, and as a final step washing for approximately one-half hour the completely nitrated oil with hot water having a temperature of substantially 65 centigrade.

2. The process of manufacturing a nitro-compound which comprises distilling coal tar at temperatures ranging approximately from to 115 Centigrade to'produce alight oil therefrom having an average specific gravity of approximately .862, then raising the specific gravity of said oil by reflux distillation to approximately .904, then treating the oil with a fat destroying solution, then prenitrating the oil at a temperature of approximately 20 Centigrade with an acid solution ing the temperature of the prenitrated oil to substantially 30 centigrade, then separating the spent acidsfrom the partially nitrated oil, then completing the prenitration of the latter bytreating and neutralizing same with a 2% caustic soda solution and allowing the prenitratedoil to settle for approximately eight hours, then completing the nitration process at a temperature of approximately 20 centigrade with an acid solution consisting approximately of 60% 152604, 35% HNOa and 5% H2O, then raising the temperature ofthe mixture to approximately 70 centigrade and maintaining such temperature for approximately ones-half hour during which period the mixture is kept in motion, then cooling the mixture to substantially 20 centigrade and allowing the same to settle for approximately four hours,

then drawing oil the nitrated oil from the spent allowing the washed nitrated oil to settle for ap- JAMES F. OBRIENJ,

approximately one-half hour, and as a final step 

